Sulfur-Containing Polymers Prepared from Fatty Acid-Derived Monomers: Application of Atom-Economical Thiol-ene/Thiol-yne Click Reactions and Inverse Vulcanization Strategies
Sulfur-Containing Polymers Prepared from Fatty Acid-Derived Monomers: Application of Atom-Economical Thiol-ene/Thiol-yne Click Reactions and Inverse Vulcanization Strategies
复制标题
脂肪酸类单体合成含硫聚合物：原子经济型硫醇-烯/硫醇-炔点击反应及逆硫化策略的应用
DOI：
10.3390/suschem1030015
复制
发表时间：
2020-10
影响因子：
--
通讯作者：
Ashlyn D. Smith;Andrew G. Tennyson;Rhett C. Smith
中科院分区：
文献类型：
--
作者：
Ashlyn D. Smith;Andrew G. Tennyson;Rhett C. Smith
本文是一篇综述，参考文献119篇。用更可持续来源的单体制成的材料取代目前使用的塑料的方法是可持续化学的最大当代挑战之一。脂肪酸是作为聚合物前体的有吸引力的候选物，因为它们可以在所有有人居住的大陆上廉价生产，并且它们也作为其他工业的未充分利用的副产品而丰富。在调查将脂肪酸转化为聚合物的一系列合成方法时，从可持续性的角度来看，那些生产有机硫聚合物的路线特别有吸引力。脂肪酸衍生的有机硫聚合物的第一种充分探索的合成方法采用硫醇-烯点击反应或密切相关的硫醇-炔变化。该方法在温和条件下具有高达100%的原子经济性和高官能团耐受性，是高产率的。最近，通过脂肪酸衍生的烯烃与元素硫的反应，反相硫化已被用于获得高硫含量的聚合物。这种方法是有吸引力的，不仅因为它在理论上是100%原子经济的，而且因为元素硫本身是化石燃料精炼的未充分利用的副产品。硫醇-烯，反硫化，和机械相关的硫醇-炔和经典的硫化，因此讨论了有前途的路线，以获得聚合物和复合材料的脂肪酸衍生的前体。
This paper is review with 119 references. Approaches to supplant currently used plastics with materials made from more sustainably-sourced monomers is one of the great contemporary challenges in sustainable chemistry. Fatty acids are attractive candidates as polymer precursors because they can be affordably produced on all inhabited continents, and they are also abundant as underutilized by-products of other industries. In surveying the array of synthetic approaches to convert fatty acids into polymers, those routes that produce organosulfur polymers stand out as being especially attractive from a sustainability standpoint. The first well-explored synthetic approach to fatty acid-derived organosulfur polymers employs the thiol-ene click reaction or the closely-related thiol-yne variation. This approach is high-yielding under mild conditions with up to 100% atom economy and high functional group tolerance. More recently, inverse vulcanization has been employed to access high sulfur-content polymers by the reaction of fatty acid-derived olefins with elemental sulfur. This approach is attractive not only because it is theoretically 100% atom economical but also because elemental sulfur is itself an underutilized by-product of fossil fuel refining. The thiol-ene, inverse vulcanization, and mechanistically-related thiol-yne and classic vulcanization are therefore discussed as promising routes to access polymers and composites from fatty acid-derived precursors.